CN105879713A - Chitosan/polyethylene glycol cross-linked gel membrane with sandwich structure and preparation method thereof - Google Patents
Chitosan/polyethylene glycol cross-linked gel membrane with sandwich structure and preparation method thereof Download PDFInfo
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- CN105879713A CN105879713A CN201410783997.2A CN201410783997A CN105879713A CN 105879713 A CN105879713 A CN 105879713A CN 201410783997 A CN201410783997 A CN 201410783997A CN 105879713 A CN105879713 A CN 105879713A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention belongs to the technical field of membrane separation and relates to a chitosan/polyethylene glycol cross-linked gel membrane with a sandwich structure and a preparation method thereof. The chitosan/polyethylene glycol cross-linked gel membrane is characterized by having the sandwich structure, wherein the upper surface layer and the lower surface are cross-linked layers, and a gel layer is arranged in the middle. The preparation method comprises the following process steps: (1) mixing chitosan, polyethylene glycol and a solvent uniformly at certain temperature, flatly laying the mixture on a polytetrafluoroethylene plate, and drying the solvent to prepare the gel membrane; (2) immersing the gel membrane in a solution containing a cross-linking agent and a catalyst for 0.5-10 hours, and carrying out surface cross-linking reaction of the gel membrane; (3) drying the cross-linked gel membrane for 24 hours in the air, then transferring into a vacuum drying box, and treating for 24 hours at the temperature of 30 DEG C to obtain the chitosan/polyethylene glycol cross-linked gel membrane with the sandwich structure. The chitosan/polyethylene glycol cross-linked gel membrane and the preparation method have the advantages that by cross linking of the upper surface layer and the lower surface layer of the membrane, the chitosan/polyethylene glycol cross-linked gel membrane with the sandwich structure is formed, and the loss of polyethylene glycol is not easy, so that the durability and the stability of the physical structure and the properties of the membrane are guaranteed. The chitosan/polyethylene glycol cross-linked gel membrane and the preparation method are applicable to separating carbon dioxide in mixed gas and recovering organic vapor.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate to a kind of sandwich structure chitosan/polyethylene glycol crosslinked gel film and
Preparation method.
Background technology
CO in current atmospheric2Concentration constantly rises, and greenhouse effect increasingly sharpens, and the ecological environment depending on the mankind for existence causes
Serious threat.Conventional CO2Isolation technics, such as amine aqueous solution absorption process, separation by deep refrigeration and pressure swing adsorption method, is realizing
Along with high energy consumption, high operating cost or the possibility that there is secondary pollution during gas separation.Therefore, there is economy, height
The membrane separation technique of the plurality of advantages such as effect, environmental protection receives more and more attention at gas separation field.
Gel film is the novel film materials of rising in recent years, high molecular polymer and functional vector collectively constitute.Polymer divides
Son forms spacial framework by effects such as crystallization, crosslinking or hydrogen bonds, holds onto liquid function carrier so that it is be uniformly dispersed
In the hole of network structure thus form stable self-supporting system.As a kind of between solid-state and and the particular matter of liquid,
Gel film has the high stability of polymeric film, and the high pass of liquid film concurrently, is separating CO2Aspect has a good application prospect.
A kind of nonionic surfactant gel gas separation membrane disclosed in Chinese patent CN102489182A and preparation method thereof, institute
Selecting functional vector is polysorbas20, Tween 80 etc., has obtained the gel film that gas permselective property can be good.Chinese patent
CN103599707A and CN103657441A discloses the preparation method of several support ionic liquid gel film, also obtains
Relatively high permeating flux and the gel film of separation selectivity.But it is poor generally to there is mechanical property in existing gel film, structural instability,
The problems such as functional vector easily spilling, are unfavorable for the industrial applications of reality.
Summary of the invention
It is an object of the invention to the deficiency overcoming existing gel film at gas separation field, it is provided that a kind of sandwich structure chitosan/
Polyethylene glycol crosslinked gel film and preparation method thereof.The present invention is by by the amino in the chitosan of gel film top layer and hydroxyl and isocyanide
Acid esters group carries out active hydrogen reaction, it is achieved the surface cross linking of gel film, forms sandwich structure.Keeping its high permeating flux
With high score on the basis of selective, it is obviously improved the mechanical property of film, has prepared and there is high permeating flux, high score from selection
Property and the cross-linked gel film of excellent mechanical performances and stability, great commercial Application potentiality.
A kind of sandwich structure chitosan/polyethylene glycol crosslinked gel film that the present invention proposes and preparation method thereof, it is characterised in that bag
Include following steps:
A is laid in poly-four after chitosan 10-20 part, solvent 70-80 part and Polyethylene Glycol 10-20 part uniformly being mixed at 30-50 DEG C
On fluorothene plate, dry out solvent, prepare gel film；
2-4 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 96-98 part normal hexane formation cross-linking agent solution by B, are soaked by above-mentioned gel film
Not in this cross-linking agent solution 0.5～10 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
Preferably, described Polyethylene Glycol is polyethylene glycol 200, Liquid Macrogol, PEG400 or Macrogol 600.
Preferably, described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexa-methylene two isocyanide
Acid esters or toluene di-isocyanate(TDI).
Preferably, described catalyst is dibutyl tin laurate.
Preferably, described solvent be mass fraction be the aqueous acetic acid of 1-3%.
Sandwich structure chitosan/polyethylene glycol crosslinked gel film that the present invention provides has three-decker, and upper layer is crosslinking
Layer, thickness is between 3-7 micron；Centre is gel layer, and thickness is between 50-70 micron.
Polymeric matrix selected by the present invention is chitosan, and this material is a kind of natural polymer biomass resource, has raw material rich
Richness, safety non-toxic, environmental protection and the plurality of advantages such as biodegradable, be dispersed with numerous character relatively on chitosan molecule chain simultaneously
Active amino and hydroxyl, lay a good foundation for its chemical modification, is a kind of preferably macromolecule polymer material.Selected function
Property carrier be Polyethylene Glycol, containing substantial amounts of ethoxy group in peg molecule, carbon dioxide is had the strongest solvability,
Safety non-toxic simultaneously, cheap, it is a kind of ideal gel material separated for gas.The sandwich structure that the present invention prepares
Chitosan/polyethylene glycol crosslinked gel film has high permeation flux and separation selectivity, simultaneously satisfactory mechanical property, and stability is excellent.
In sum, sandwich structure chitosan/polyethylene glycol crosslinked gel film of the present invention and preparation method thereof has following
Advantage:
1, the chitosan aboundresources that the present invention selects, low price, safety and environmental protection, chemically reactive modification, biodegradable.
2, the Polyethylene Glycol that the present invention uses has extremely strong dissolving selectivity to carbon dioxide, and the most nontoxic non-stimulated, structure is more steady
Fixed.
3, the cross-linking process of inventive gel film relates to interfacial reaction, and top layer is cross-linked layer, and even compact improves good mechanics
Performance and stability；Centre is gel layer, is full of Polyethylene Glycol, it is provided that high permeating flux and separation selectivity.
Detailed description of the invention:
The following is the embodiment of sandwich structure chitosan/polyethylene glycol crosslinked gel film and preparation method thereof, but described embodiment is not
It is construed as limiting the invention.
Embodiment one:
(1) gel film is prepared:
Aqueous acetic acid and 15 parts of polyethylene glycol 200s that 10 parts of chitosans, 75 parts of mass fractions are 2% are mixed at 50 DEG C
It is laid in after Jun Yun on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
3 parts of toluene di-isocyanate(TDI)s and 2 dibutyl tin laurates are dissolved in 97 parts of normal hexane formation cross-linking agent solution, will
Above-mentioned gel film is immersed in this cross-linking agent solution 0.5 hour, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
Above-mentioned sandwich structure chitosan/polyethylene glycol crosslinked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa
Under test condition, CO2Infiltration coefficient be 247barrer, CO2/N2Ideal selectivity be 72.39.
Embodiment two:
(1) gel film is prepared:
Aqueous acetic acid and 10 parts of Liquid Macrogols that 10 parts of chitosans, 80 parts of mass fractions are 3% are mixed at 30 DEG C
It is laid in after Jun Yun on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
4 parts of isophorone diisocyanate and 1 dibutyl tin laurate are dissolved in 96 parts of normal hexane formation cross-linking agent molten
Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 10 hours, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
Above-mentioned sandwich structure chitosan/polyethylene glycol crosslinked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa
Under test condition, CO2Infiltration coefficient be 198barrer, CO2/N2Ideal selectivity be 93.56.
Embodiment three:
(1) gel film is prepared:
Aqueous acetic acid and 10 parts of Macrogol 600s that 20 parts of chitosans, 70 parts of mass fractions are 1% are mixed at 30 DEG C
It is laid in after Jun Yun on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
3 parts of hexamethylene diisocyanates and 1 dibutyl tin laurate are dissolved in 97 parts of normal hexane formation cross-linking agent molten
Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 3 hours, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
Above-mentioned sandwich structure chitosan/polyethylene glycol crosslinked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa
Under test condition, CO2Infiltration coefficient be 136barrer, CO2/N2Ideal selectivity be 113.68.
Embodiment four:
(1) gel film is prepared:
Aqueous acetic acid and 20 parts of PEG400s that 10 parts of chitosans, 70 parts of mass fractions are 2% are mixed at 40 DEG C
It is laid in after Jun Yun on polyfluortetraethylene plate, dry out solvent, prepares gel film.
(2) film top layer cross-links again:
2 parts of methyl diphenylene diisocyanates and 2 dibutyl tin laurates are dissolved in 98 parts of normal hexane formation cross-linking agent molten
Liquid, is immersed in above-mentioned gel film in this cross-linking agent solution 1 hour, carries out gel film surface cross linking；
(3) post processing:
Gel film after crosslinking is dried 24 hours in atmosphere, then proceeds in vacuum drying oven, process 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
Above-mentioned sandwich structure chitosan/polyethylene glycol crosslinked gel film is used for CO2/N2Separate, at 30 DEG C and 0.06MPa
Under test condition, CO2Infiltration coefficient be 253barrer, CO2/N2Ideal selectivity be 64.39.
The description of above-described embodiment should be considered explanation, it is easy to is understood by, can be without departing from illustrating the most in detail in the claims
The present invention in the case of use many changes and the combination of feature described above, this kind of change has been not to be regarded as a departure from this
Bright spirit and scope, and all such change be included in the range of claims below.
Claims (6)
1. the preparation method of sandwich structure chitosan/polyethylene glycol crosslinked gel film, it is characterised in that comprise the steps:
A is laid in poly-four after chitosan 10-20 part, solvent 70-80 part and Polyethylene Glycol 10-20 part uniformly being mixed at 30-50 DEG C
On fluorothene plate, dry out solvent, prepare gel film；
2-4 part cross-linking agent and 1-2 are dripped catalyst and are dissolved in 96-98 part normal hexane formation cross-linking agent solution by B, are soaked by above-mentioned gel film
Not in this cross-linking agent solution 0.5～10 hour, carry out gel film surface cross linking；
Gel film after crosslinking is dried 24 hours by C in atmosphere, then proceeds in vacuum drying oven, processes 24 hours at 30 DEG C,
Obtain sandwich structure chitosan/polyethylene glycol crosslinked gel film.
The preparation method of sandwich structure chitosan/polyethylene glycol crosslinked gel film the most according to claim 1, it is characterised in that
Described Polyethylene Glycol is polyethylene glycol 200, Liquid Macrogol, PEG400 or Macrogol 600.
3. according to the preparation method of sandwich structure chitosan/polyethylene glycol crosslinked gel film described in claim 1-2, it is characterised in that
Described cross-linking agent is methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or toluene two
Isocyanates.
4. according to the preparation method of sandwich structure chitosan/polyethylene glycol crosslinked gel film described in claim 1-3, it is characterised in that
Described catalyst is dibutyl tin laurate.
5. according to the preparation method of sandwich structure chitosan/polyethylene glycol crosslinked gel film described in claim 1-4, it is characterised in that
Described solvent be mass fraction be the aqueous acetic acid of 1-3%.
6. sandwich structure chitosan/polyethylene glycol crosslinked gel film, it is characterised in that described gel film has three-decker,
Upper layer is cross-linked layer, and thickness is between 3-7 micron；Centre is gel layer, and thickness is between 50-70 micron.
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| CN201410783997.2A CN105879713B (en) | 2014-12-16 | 2014-12-16 | A kind of sandwich structure chitosan/polyethylene glycol crosslinked gel mould and preparation method thereof |
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| CN201410783997.2A CN105879713B (en) | 2014-12-16 | 2014-12-16 | A kind of sandwich structure chitosan/polyethylene glycol crosslinked gel mould and preparation method thereof |
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| CN105879713A true CN105879713A (en) | 2016-08-24 |
| CN105879713B CN105879713B (en) | 2019-07-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101720257A (en) * | 2007-05-26 | 2010-06-02 | 斯托尼布鲁克水净化公司 | High flux fluid separation membranes comprising a cellulose or cellulose derivative layer |
| CN103242554A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院化学研究所 | Nanometer plural gel and preparation method thereof |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
| CN104014255A (en) * | 2014-06-05 | 2014-09-03 | 北京工业大学 | Preparation method for self-assembled modified silicone rubber/inorganic particle alcohol permselective hybrid membrane |
-
2014
- 2014-12-16 CN CN201410783997.2A patent/CN105879713B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101720257A (en) * | 2007-05-26 | 2010-06-02 | 斯托尼布鲁克水净化公司 | High flux fluid separation membranes comprising a cellulose or cellulose derivative layer |
| CN103242554A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院化学研究所 | Nanometer plural gel and preparation method thereof |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
| CN104014255A (en) * | 2014-06-05 | 2014-09-03 | 北京工业大学 | Preparation method for self-assembled modified silicone rubber/inorganic particle alcohol permselective hybrid membrane |
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